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While the direct, one‐step conversion of meso‐tetrakis(pentafluorophenyl)porphyrin to its corresponding bacteriodilactone is well established, no such reaction has been achieved for meso‐tetraphenyl or meso‐tetrakis(4‐trifluoromethylphenyl)porphyrin. Thus, we describe two stepwise oxidation approaches of these porphyrins toward the corresponding bacteriodilactones, as mixtures of two inseparable regioisomers. As shown by 1H NMR spectroscopy, the ratio of the two isomers is oxidant‐dependent. Their ZnII and PdII complexes were formed by metal ion insertion into the free bases. Some of the free base dilactones and their metal complexes were also characterized crystallographically, demonstrating the planarity of the macrocycle. This report makes these intriguing porphyrinoids synthetically accessible for further study. [ABSTRACT FROM AUTHOR]

meso-Phenyl- and meso-pentafluorophenyl-porpholactones, their metal complexes, as well as porphyrinoids directly derived from them are useful in a number of technical and biomedical applications, and more uses are expected to be discovered. About a dozen competing and complementary pathways toward their synthesis were reported. The suitability of the methods changes with the meso-aryl group and whether the free base or metal derivatives are sought. These circumstances make it hard for anyone outside of the field of synthetic porphyrin chemistry to ascertain which pathway is the best to produce which specific derivative. We report here on what we experimentally evaluated to be the most efficient pathways to generate the six key compounds from the commercially available porphyrins, meso-tetraphenylporphyrin (TPP) and meso-tetrakis(pentafluorophenyl)porphyrin (TFPP): free base meso-tetraphenylporpholactone (TPL) and meso-tetrakis(pentafluorophenyl)porpholactone (TFPL), and their platinum(II) and zinc(II) complexes TPLPt, TFPLPt, TPLZn, and TFPLZn, respectively. Detailed procedures are provided to make these intriguing molecules more readily available for their further study. [ABSTRACT FROM AUTHOR]